Low viscosity low volatility lubricating oil base stocks and processes for preparing same

ABSTRACT

A composition that includes one or more compounds represented by the formula
 
R 1 —O—R 2  
 
wherein R 1  is a substituted or unsubstituted aryl or polyaryl group having from about 4 to about 40 carbon atoms, and R 2  is the residue of a substituted or unsubstituted glycol ether having from about 4 to about 40 carbon atoms. The composition has a viscosity (Kv 100 ) from about 1 to about 10 cSt at 100° C. as determined by ASTM D-445, a viscosity index (VI) from about −100 to about 300 as determined by ASTM D-2270, and a Noack volatility of no greater than 50 percent as determined by ASTM D-5800. The disclosure also relates to a process for producing the composition, a lubricating oil base stock and lubricating oil containing the composition, and a method for improving one or more of oxidative stability, solubility and dispersancy of polar additives of a lubricating oil by using as the lubricating oil a formulated oil containing the composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 62/254,750 filed Nov. 13, 2015, which is herein incorporated byreference in its entirety. This application is related to one otherco-pending U.S. application Ser. No. 15/297,292, filed on even dateherewith, and entitled “Low Viscosity Low Volatility Lubricating OilBase Stocks And Processes For Preparing Same.” This co-pending U.S.application is hereby incorporated by reference herein in its entirety.

FIELD

This disclosure relates to low viscosity, low volatility compositionsthat include one or more glycol ether substituted aryl compounds, aprocess for producing the compositions, a lubricating oil base stock andlubricating oil containing the composition, and a method for improvingone or more of fuel economy, oxidative stability, hydrolytic stability,solubility and dispersancy of polar additives of a lubricating oil byusing as the lubricating oil a formulated oil containing thecomposition.

BACKGROUND

Lubricants in commercial use today are prepared from a variety ofnatural and synthetic base stocks admixed with various additive packagesand solvents depending upon their intended application. The base stockstypically include mineral oils, polyalphaolefins (PAO), gas-to-liquidbase oils (GTL), silicone oils, phosphate esters, diesters, polyolesters, and the like.

A major trend for passenger car engine oils (PCEOs) is an overallimprovement in quality as higher quality base stocks become more readilyavailable. Typically the highest quality PCEO products are formulatedwith base stocks such as PAOs or GTL stocks admixed with variousadditive packages.

For improving fuel economy, base oil viscosity is very important.Substantial improved fuel economy (>2%) requires breakthrough in: (1)base oil volatility (2) durability and (3) friction. Friction lossesoccur between the moving components within the engine. Models developedto date indicate that fuel economy is heavily influenced by thelubricant properties at high shear. The base stock contributes a greaterproportion of the total viscosity under high shear conditions than underlow shear. Lowering base stock viscosity is likely to have the largestimpact on future fuel economy gains.

Current commercial PAO fluids (e.g., SpectraSyn™ 2) based on hydrocarbonand commercial esters (e.g., 2-ethylhexyl adipate, di-2-ethylhexylazelate, Esterex™ A32, Esterex™ A34) do not adequately allow formulationof ultra-low viscosity lubricant while still meeting API specification(e.g., Noack volatility of 15% or less). In order to formulate ultra-lowviscosity lubricant for fuel economy benefit, it is desirable to havelow viscosity and low volatility properties co-exist in the same basestock, for meeting volatility requirement. In addition, the base stockshould also possess adequate thermal and oxidative stability at hightemperature to prevent or minimize deposit formation. Good compatibilitywith additives commonly used in lubricant formulations (PVL, CVL,industrial lubricants), good low temperature properties, and acceptableviscosity indices are also necessary for the base stocks.

Poly-α-olefins (PAOs) are important lube base stocks with many excellentlubricant properties, including high viscosity index (VI), lowvolatility and are available in various viscosity range (Kv₁₀₀ 2-300cSt). However, PAOs are paraffinic hydrocarbons with low polarity. Thislow polarity leads to low solubility and dispersancy for polar additivesor sludge generated during service. To compensate for this low polarity,lube formulators usually add one or multiple polar cobase stocks. Esteror alkylated naphthalene (AN) is usually present at 1 wt. % to 50 wt. %levels in many finished lubricant formulations to increase the fluidpolarity which improves the solubility of polar additives and sludge.

Therefore, there is a need for polar cobase fluids that provideappropriate solubility and dispersibility for polar additives or sludgegenerated during service of lubricating oils.

Future automotive and industrial trend suggest that there will be a needfor advanced additive technology and synthetic base stocks withsubstantially better thermal and oxidative stability. This is primarilybecause of smaller sump sizes that will have more thermal and oxidativestresses on the lubricants. Performance requirements have become morestringent in the past 10 to 20 years and the demand for longer drainintervals has grown steadily. Also, the use of Group II, III and IV baseoils is becoming more widespread. Such base oils have very little sulfurcontent since natural sulfur-containing antioxidants are either absentor removed during the severe refining process.

It is known that lubricant oils used in internal combustion engines andtransmission of automobile engines or trucks are subjected to demandingenvironments during use. These environments result in the lubricantsuffering oxidation catalyzed by the presence of impurities in the oil,such as iron (wear) compounds and elevated temperatures. The oxidationmanifests itself by increase in acid or viscosity and deposit formationor any combination of these symptoms. These are controlled to someextent by the use of antioxidants which can extend the useful life ofthe lubricating oil, particularly by reducing or preventing unacceptableviscosity increases. Besides oxidation inhibition, other parameters suchas rust and wear control are also important.

A major challenge in engine oil formulation is simultaneously achievingimproved fuel economy while also achieving appropriate solubility anddispersibility for polar additives or sludge generated during service oflubricating oils and oxidative stability and hydrolytic stability.

Therefore, there is need for better additive and base stock technologyfor lubricant compositions that will meet ever more stringentrequirements of lubricant users. In particular, there is a need foradvanced additive technology and synthetic base stocks with improvedfuel economy, solubility and dispersibility for polar additives orsludge generated during service of lubricating oils, hydrolyticstability, and oxidative stability.

The present disclosure also provides many additional advantages, whichshall become apparent as described below.

SUMMARY

This disclosure provides compositions that include one or more glycolether substituted aryl compounds that have desirable low viscosity/lowvolatility properties while exhibiting good high-temperaturethermal-oxidative stability. Thus, the compositions of this disclosureprovide a solution to achieve enhanced fuel economy and energyefficiency. In addition, good solvency for commonly used polar additivesand potentially good hydrolytic and oxidative stability are otheradvantages of these compounds in base stock applications.

This disclosure relates in part to a composition comprising one or morecompounds represented by the formulaR₁—O—R₂wherein R₁ is a substituted or unsubstituted aryl or polyaryl grouphaving from about 4 to about 40 carbon atoms, and R₂ is the residue of asubstituted or unsubstituted glycol ether having from about 4 to about40 carbon atoms. The composition has a viscosity (Kv₁₀₀) from about 1 toabout 10 at 100° C. as determined by ASTM D-445, a viscosity index (VI)from about −100 to about 300 as determined by ASTM D-2270, and a Noackvolatility of no greater than 50 percent as determined by ASTM D-5800.

This disclosure also relates in part to a composition comprising one ormore glycol ether substituted aryl compounds represented by the formulaR₁—O—R₂wherein R₁ is a substituted or unsubstituted aryl or polyaryl grouphaving from about 4 to about 40 carbon atoms, and R₂ is the residue of asubstituted or unsubstituted glycol ether having from about 4 to about40 carbon atoms. The composition has a viscosity (Kv₁₀₀) from about 1 toabout 10 at 100° C. as determined by ASTM D-445, a viscosity index (VI)from about −100 to about 300 as determined by ASTM D-2270, and a Noackvolatility of no greater than 50 percent as determined by ASTM D-5800.The one or more glycol ether substituted aryl compounds are produced bya process comprising reacting a substituted or unsubstituted aryl halidewith a substituted or unsubstituted glycol ether, optionally in thepresence of a catalyst, under reaction conditions sufficient to producesaid one or more glycol ether substituted aryl compounds.

This disclosure further relates in part to a composition comprising oneor more glycol ether substituted aryl compounds represented by theformulaR₁—O—R₂wherein R₁ is a substituted or unsubstituted aryl or polyaryl grouphaving from about 4 to about 40 carbon atoms, and R₂ is the residue of asubstituted or unsubstituted glycol ether having from about 4 to about40 carbon atoms. The composition has a viscosity (Kv₁₀₀) from about 1 toabout 10 at 100° C. as determined by ASTM D-445, a viscosity index (VI)from about −100 to about 300 as determined by ASTM D-2270, and a Noackvolatility of no greater than 50 percent as determined by ASTM D-5800.The one or more glycol ether substituted aryl compounds are produced bya process comprising reacting a substituted or unsubstituted arylalcohol with a substituted or unsubstituted glycol ether halide,optionally in the presence of a catalyst, under reaction conditionssufficient to produce the one or more glycol ether substituted arylcompounds.

This disclosure yet further relates in part to a lubricating oil basestock comprising one or more compounds represented by the formulaR₁—O—R₂wherein R₁ is a substituted or unsubstituted aryl or polyaryl grouphaving from about 4 to about 40 carbon atoms, and R₂ is the residue of asubstituted or unsubstituted glycol ether having from about 4 to about40 carbon atoms. The lubricating oil base stock has a viscosity (Kv₁₀₀)from about 1 to about 10 at 100° C. as determined by ASTM D-445, aviscosity index (VI) from about −100 to about 300 as determined by ASTMD-2270, and a Noack volatility of no greater than 50 percent asdetermined by ASTM D-5800.

This disclosure also relates in part to a lubricating oil comprising alubricating oil base stock as a major component, and a glycol ethersubstituted aryl compound cobase stock as a minor component. The glycolether substituted aryl compound cobase stock comprises one or morecompounds represented by the formulaR₁—O—R₂wherein R₁ is a substituted or unsubstituted aryl or polyaryl grouphaving from about 4 to about 40 carbon atoms, and R₂ is the residue of asubstituted or unsubstituted glycol ether having from about 4 to about40 carbon atoms. The lubricating oil has a viscosity (Kv₁₀₀) from about1 to about 10 at 100° C. as determined by ASTM D-445, a viscosity index(VI) from about −100 to about 300 as determined by ASTM D-2270, and aNoack volatility of no greater than 50 percent as determined by ASTMD-5800.

This disclosure further relates in part to a method for improving one ormore of oxidative stability, solubility and dispersancy of polaradditives of a lubricating oil by using as the lubricating oil aformulated oil comprising a lubricating oil base stock as a majorcomponent, and a glycol ether substituted aryl compound cobase stock asa minor component. The glycol ether substituted aryl compound cobasestock comprises one or more compounds represented by the formulaR₁—O—R₂wherein R₁ is a substituted or unsubstituted aryl or polyaryl grouphaving from about 4 to about 40 carbon atoms, and R₂ is the residue of asubstituted or unsubstituted glycol ether having from about 4 to about40 carbon atoms. The lubricating oil has a viscosity (Kv₁₀₀) from about1 to about 10 at 100° C. as determined by ASTM D-445, a viscosity index(VI) from about −100 to about 300 as determined by ASTM D-2270, and aNoack volatility of no greater than 50 percent as determined by ASTMD-5800.

It has been surprisingly found that outstanding low viscosity lowvolatility properties, good high-temperature thermal and oxidativestability, good solvency for polar additives, and traction benefits, canbe attained in an engine lubricated with a lubricating oil by using asthe lubricating oil a formulated oil in accordance with this disclosure.In particular, a lubricating oil base stock comprising one or moreglycol ether substituted aryl compounds exhibits low viscosity, lowvolatility, desired solvency for polar additives, and superior oxidativestability, which helps to prolong the useful life of lubricants andsignificantly improve the durability and resistance of lubricants whenexposed to high temperatures. The lubricating oils of this disclosureare particularly advantageous as passenger vehicle engine oil (PVEO)products.

Further objects, features and advantages of the present disclosure willbe understood by reference to the following drawings and detaileddescription.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows kinematic viscosities, viscosity indices (VI) andvolatility of Group V base stocks of Examples 1-7 in accordance withExample 8.

FIG. 2 graphically shows kinematic viscosity at 100° C. (x-axis) andthermogravimetric analysis (TGA) Noack (y-axis) of PAO4, mPAO3.4, PAO2,mPAO2 and synthetic fluids of Examples 1-7 in accordance with Example 8.

DETAILED DESCRIPTION

All numerical values within the detailed description and the claimsherein are modified by “about” or “approximately” the indicated value,and take into account experimental error and variations that would beexpected by a person having ordinary skill in the art.

The compositions of this disclosure contain an aryl group and etherfunctionality. These compositions exhibit (1) outstanding low viscositylow volatility properties, (2) good high-temperature thermal andoxidative stability, (3) good hydrolytic stability, (4) good solvencyfor polar additives, and (5) traction benefits, which make themattractive as Group V synthetic base stocks in high performance, fueleconomy lubricant applications.

The compositions of this disclosure are oxygen-containing Group V basestocks that exhibit hydrolytic stability. Unlike Group V esters, thebase stocks of this disclosure are hydrolytically stable. Unlikealkylated naphthalene Group V base stocks, the base stocks of thisdisclosure contain oxygen functionality and are more polar.

Low viscosity base stocks (e.g., kinematic viscosity at 100° C., 2-3cSt) currently available in the marketplace are too volatile(Noack >15-20%) to be used for formulating next-generation ultra-lowviscosity engine oils (i.e., xxW-4→xxW-16). These base stocks (e.g.,SpectraSyn™ 2, GTL3, bis(2-ethylhexyl) adipate, di-2-ethylhexyl azelate,Esterex™ A32) are unable to provide formulated engine oils that alsomeet current volatility API specification. In addition, current Group Vester base stocks generally have poor high temperature oxidationstability which can cause operational problems in engine, potentiallycausing high deposit formation. The present disclosure identifies glycolether substituted aryl compounds that have desirable low viscosity andlow volatility properties while exhibiting traction benefits, gooddeposit control behavior and good high-temperature thermal-oxidativestability, hence provides a solution to achieve enhanced fuel economyand energy efficiency. In addition, good solvency for commonly usedpolar additives and potentially good hydrolytic stability are otheradvantages of these compounds in base stock applications.

In accordance with this disclosure, the residue of a glycol ether chainis attached to an aryl group (e.g., naphthalene, benzene, diphenylether,diphenylamine, and the like) to obtain Group V fluids. By changing theglycol ether residue portion, molecules with varying polarity (andhydrocarbon compatibility) can be synthesized. Traditional Group Vfluids, such as alkylated naphthalene (AN), are prepared via acidcatalyst alkylation reaction that tends to give mixed alkylatedproducts. The fluids of this disclosure are precise molecules. Thesemolecules can be used base stocks or as cobase stocks along with mPAO(metallocene catalyst based poly-alpha-olefin), PAO, Group I-III+, GTL,ionic liquids, and the like.

As indicated above, glycol ether substituted aryl compound base stockand cobase stock components useful in this disclosure include, forexample, compositions containing one or more compounds represented bythe formulaR₁—O—R₂wherein R₁ is a substituted or unsubstituted aryl or polyaryl grouphaving from about 4 to about 40 carbon atoms, and R₂ is the residue of asubstituted or unsubstituted glycol ether having from about 4 to about40 carbon atoms. The composition has a viscosity (Kv₁₀₀) from about 1 toabout 10 at 100° C. as determined by ASTM D-445, a viscosity index (VI)from about −100 to about 300 as determined by ASTM D-2270, and a Noackvolatility of no greater than 50 percent as determined by ASTM D-5800.

Preferred glycol ether substituted aryl compound base stock and cobasestock components include those in which R₁ is substituted orunsubstituted phenyl, benzyl, naphthyl, or diphenyl (e.g., diphenylamine or diphenyl ether), and R₂ is the residue of a substituted orunsubstituted glycol ether (C₄-C₄₀).

Preferred glycol ether substituted aryl compound base stock and cobasestock components have a viscosity (Kv₁₀₀) from about 1 to about 8, morepreferably from about 2 to about 6, at 100° C. as determined by ASTMD-445, a viscosity index (VI) from about −100 to about 300, morepreferably from about 0 to about 150, even more preferably from about 25to about 100, as determined by ASTM D-2270, and a Noack volatility of nogreater than 75 percent, more preferably no greater than 50 percent,even more preferably no greater than 15 percent, as determined by ASTMD-5800.

Illustrative glycol ether substituted aryl compound base stock andcobase stock components useful in the present disclosure comprise one ormore compounds represented by the formulae

wherein R is a substituted or unsubstituted alkyl group having fromabout 4 to about 40 carbon atoms; and n is a value from about 1 to about12;

wherein R is a substituted or unsubstituted alkyl group having fromabout 4 to about 40 carbon atoms, n is a value from about 1 to about 12;and X is CH₂, O, NR′ or S, wherein R′ is hydrogen or an alkyl grouphaving from 1 to about 4 carbon atoms; and

wherein R is a substituted or unsubstituted alkyl group having fromabout 4 to about 40 carbon atoms; and n is a value from about 1 to about12.

Illustrative glycol ether substituted aryl compound base stock andcobase stock components useful in the present disclosure include, forexample, 1-((2-(2-(hexyloxy)ethoxy)ethoxy)naphthalene,

-   2-(2-(2-(dodecyloxy)ethoxy)ethoxy)benzene,-   (2-(2-hexyloxy)ethoxy)ethoxy)benzene,    1-(2-(2-(hexyloxy)ethoxy)ethoxy)-4-methylbenzene,    4-(2-(2-(hexyloxy)ethoxy)ethoxy)-1,2-dimethylbenzene,-   4-(2-(2-(hexyloxy)ethoxy)ethoxy)-N-phenylaniline,-   1-(2-(2-(hexyloxy)ethoxy)ethoxy)-4-phenoxybenzene,-   1-(2-(2-butoxyethoxy)ethoxy)naphthalene,-   3-(2-ethoxyethoxyethoxy)-2,6-diphenylmethane, and the like.

Illustrative glycol ether substituted aryl compound base stock andcobase stock components useful in the present disclosure include, forexample, the product of reacting a substituted or unsubstituted arylhalide with a substituted or unsubstituted glycol ether, optionally inthe presence of a catalyst, under reaction conditions sufficient toproduce said one or more glycol ether substituted aryl compounds.

Reaction conditions for the reaction of the aryl halide with the glycolether, such as temperature, pressure and contact time, may also varygreatly and any suitable combination of such conditions may be employedherein. The reaction temperature may range between about 25° C. to about250° C., and preferably between about 30° C. to about 200° C., and morepreferably between about 60° C. to about 150° C. Normally the reactionis carried out under ambient pressure and the contact time may vary froma matter of seconds or minutes to a few hours or greater. The reactantscan be added to the reaction mixture or combined in any order. The stirtime employed can range from about 0.5 to about 48 hours, preferablyfrom about 1 to 36 hours, and more preferably from about 2 to 24 hours.

Illustrative aryl halides useful in the process of this disclosureinclude, for example,

-   1-iodonaphthalene, iodobenzene, 1-iodo-4-methylbenzene,    4-iodo,1-2-dimethylbenzene, 4-bromodiphenylamine,    4-bromodiphenylether,-   3-bromodiphenylamine, 2-iodotoluene, 3-iodotoluene,    1-bromo-2,3,-dimethylbenzene, 1-bromo-2,4,-dimethylbenzene,    1-bromo-2-ethylbenzene,-   1-bromo-4-ethylbenzene, 2-bromo-1,3-dimethylbenzene,-   2-bromo-1,4-dimethylbenzene, 2-bromo-1,2 dimethylbenzene,    1-bromo-2-ethoxybenzene, 1-iodo-3,4-dimethylbenzene,    1-iodo-3,5-dimethylbenzene,-   2-iodo-1,3-dimethylbenzene, 7-bromo-1H-indene,    1-bromo-3-isopropylbenzene,-   1-bromo-4-isopropylbenzene, 1-iodo-4-isopropylbenzene, 2-iodocumene,-   5-iodo-1,2,3,-trimethylbenzene, 1-bromo-3-(trimethylsiliyl)benzene,    1-bromo-4-(trimethylsiliyl)benzene, 2-bromonapthalene,    2-iodonapthalene, 1-bromo-4-tert.butylbenzene,    1-iodo-4-tertbutylbenzene, 1-bromo-4-methylnapthalene.-   1-bromo-2-methylnapthalene, 2-bromobiphenyl, 4-bromobiphenyl,-   3-bromobiphenyl, 3-bromophenathrene, 2-bromofluorene,    9-bromofluorene,-   9-bromoanthracene, 9-bromophenathrene, 9-iodophenathrene,    1-bromo-3,5-tert-butylbenzene, 1-bromopyrene, and the like.

Illustrative glycol ethers useful in the process of this disclosureinclude, for example, di(ethylene glycol)butyl ether, di(ethyleneglycol) hexyl ether, di(ethylene glycol) dodecyl ether, and the like.

Other illustrative glycol ethers include, for example, di(ethyleneglycol) monohexyl ether, tri(ethylene glycol) monomethyl ether,tri(propylene glycol) monomethyl ether, tri(ethylene glycol) monoethylether, tri(ethylene glycol) monobutyl ether, di(ethylene glycol)monoethyl ether, di(ethylene glycol) monobutyl ether, tri(propyleneglycol) monopropyl ether, tri(propylene glycol) monobutyl ether,poly(ethylene glycol) dodecyl ether (Brij 30), ethylene glycolmono-2-ethylhexyl ether, and the like. By changing the glycol ethermolecules, the fluid can be synthesized with various polarity.

Illustrative glycol ether substituted aryl compound base stock andcobase stock components useful in the present disclosure include, forexample, the product of reacting a substituted or unsubstituted arylalcohol with a substituted or unsubstituted glycol ether halide,optionally in the presence of a catalyst, under reaction conditionssufficient to produce said one or more glycol ether substituted arylcompounds.

Reaction conditions for the reaction of the aryl alcohol with the glycolether halide, such as temperature, pressure and contact time, may alsovary greatly and any suitable combination of such conditions may beemployed herein. The reaction temperature may range between about 25° C.to about 250° C., and preferably between about 30° C. to about 200° C.,and more preferably between about 60° C. to about 150° C. Normally thereaction is carried out under ambient pressure and the contact time mayvary from a matter of seconds or minutes to a few hours or greater. Thereactants can be added to the reaction mixture or combined in any order.The stir time employed can range from about 0.5 to about 48 hours,preferably from about 1 to 36 hours, and more preferably from about 2 to24 hours.

Illustrative aryl alcohols useful in the process of this disclosureinclude, for example, 4-benzylphenol, 5,6,7,8,-tetrahydro-1-napthol,5,6,7,8,-tetrahydro-2-napthol, 2-napthol, 1-napthol, 2-benzylphenol,4-phenoxyphenol, 2-methyl-1-napthol, 6-methoxy-2-napthol,3-methoxy-2-napthol, 7-methoxy-2-napthol, 3-phenylphenol,2-phenylphenol, 4-phenylphenol, and the like.

Illustrative glycol ether halides useful in the process of thisdisclosure include, for example, 2-(2-ethoxyethoxy)ethyl bromide, andthe like. By changing the glycol ether halide molecules, the fluid canbe synthesized with various polarity.

Examples of techniques that can be employed to characterize thecompositions formed by the process described above include, but are notlimited to, analytical gas chromatography, nuclear magnetic resonance,thermogravimetric analysis (TGA), inductively coupled plasma massspectrometry, differential scanning calorimetry (DSC), volatility andviscosity measurements.

This disclosure provides lubricating oils useful as engine oils and inother applications characterized by excellent oxidative stability. Thelubricating oils are based on high quality base stocks including a majorportion of a hydrocarbon base fluid such as a PAO or GTL with asecondary cobase stock component which is a glycol ether substitutedaryl compound as described herein. The lubricating oil base stock can beany oil boiling in the lube oil boiling range, typically between about100 to 450° C. In the present specification and claims, the terms baseoil(s) and base stock(s) are used interchangeably.

The viscosity-temperature relationship of a lubricating oil is one ofthe critical criteria which must be considered when selecting alubricant for a particular application. Viscosity Index (VI) is anempirical, unitless number which indicates the rate of change in theviscosity of an oil within a given temperature range. Fluids exhibitinga relatively large change in viscosity with temperature are said to havea low viscosity index. A low VI oil, for example, will thin out atelevated temperatures faster than a high VI oil. Usually, the high VIoil is more desirable because it has higher viscosity at highertemperature, which translates into better or thicker lubrication filmand better protection of the contacting machine elements.

In another aspect, as the oil operating temperature decreases, theviscosity of a high VI oil will not increase as much as the viscosity ofa low VI oil. This is advantageous because the excessive high viscosityof the low VI oil will decrease the efficiency of the operating machine.Thus high VI (HVI) oil has performance advantages in both high and lowtemperature operation. VI is determined according to ASTM method D2270-93 [1998]. VI is related to kinematic viscosities measured at 40°C. and 100° C. using ASTM Method D 445-01.

Lubricating Oil Base Stocks

A wide range of lubricating oils is known in the art. Lubricating oilsthat are useful in the present disclosure are both natural oils andsynthetic oils. Natural and synthetic oils (or mixtures thereof) can beused unrefined, refined, or rerefined (the latter is also known asreclaimed or reprocessed oil). Unrefined oils are those obtaineddirectly from a natural or synthetic source and used without addedpurification. These include shale oil obtained directly from retortingoperations, petroleum oil obtained directly from primary distillation,and ester oil obtained directly from an esterification process. Refinedoils are similar to the oils discussed for unrefined oils except refinedoils are subjected to one or more purification steps to improve the atleast one lubricating oil property. One skilled in the art is familiarwith many purification processes. These processes include solventextraction, secondary distillation, acid extraction, base extraction,filtration, and percolation. Rerefined oils are obtained by processesanalogous to refined oils but using an oil that has been previously usedas a feed stock.

Groups I, II, III, IV and V are broad categories of base oil stocksdeveloped and defined by the American Petroleum Institute (APIPublication 1509; www.API.org) to create guidelines for lubricant baseoils. Group I base stocks generally have a viscosity index of betweenabout 80 to 120 and contain greater than about 0.03% sulfur and lessthan about 90% saturates. Group II base stocks generally have aviscosity index of between about 80 to 120, and contain less than orequal to about 0.03% sulfur and greater than or equal to about 90%saturates. Group III stock generally has a viscosity index greater thanabout 120 and contains less than or equal to about 0.03% sulfur andgreater than about 90% saturates. Group IV includes polyalphaolefins(PAO). Group V base stocks include base stocks not included in GroupsI-IV. The table below summarizes properties of each of these fivegroups.

Base Oil Properties Saturates Sulfur Viscosity Index Group I   <90and/or  >0.03% and ≧80 and <120 Group II ≧90 and ≦0.03% and ≧80 and <120Group III ≧90 and ≦0.03% and ≧120 Group IV Includes polyalphaolefins(PAO) products Group V All other base oil stocks not included in GroupsI, II, III or IV

Natural oils include animal oils, vegetable oils (castor oil and lardoil, for example), and mineral oils. Animal and vegetable oilspossessing favorable thermal oxidative stability can be used. Of thenatural oils, mineral oils are preferred. Mineral oils vary widely as totheir crude source, for example, as to whether they are paraffinic,naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal orshale are also useful in the present disclosure. Natural oils vary alsoas to the method used for their production and purification, forexample, their distillation range and whether they are straight run orcracked, hydrorefined, or solvent extracted.

Group II and/or Group III hydroprocessed or hydrocracked base stocks, aswell as synthetic oils such as polyalphaolefins, alkyl aromatics andsynthetic esters, i.e. Group IV and Group V oils are also well knownbase stock oils.

Synthetic oils include hydrocarbon oil such as polymerized andinterpolymerized olefins (polybutylenes, polypropylenes, propyleneisobutylene copolymers, ethylene-olefin copolymers, andethylene-alphaolefin copolymers, for example). Polyalphaolefin (PAO) oilbase stocks, the Group IV API base stocks, are a commonly used synthetichydrocarbon oil. By way of example, PAOs derived from C₈, C₁₀, C₁₂, C₁₄olefins or mixtures thereof may be utilized. See U.S. Pat. Nos.4,956,122; 4,827,064; and 4,827,073, which are incorporated herein byreference in their entirety. Group IV oils, that is, the PAO base stockshave viscosity indices preferably greater than 130, more preferablygreater than 135, still more preferably greater than 140.

Esters in a minor amount may be useful in the lubricating oils of thisdisclosure. Additive solvency and seal compatibility characteristics maybe secured by the use of esters such as the esters of dibasic acids withmonoalkanols and the polyol esters of monocarboxylic acids. Esters ofthe former type include, for example, the esters of dicarboxylic acidssuch as phthalic acid, succinic acid, sebacic acid, fumaric acid, adipicacid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenylmalonic acid, etc., with a variety of alcohols such as butyl alcohol,hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc. Specificexamples of these types of esters include dibutyl adipate,di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate,diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecylphthalate, dieicosyl sebacate, etc.

Particularly useful synthetic esters are those which are obtained byreacting one or more polyhydric alcohols, preferably the hinderedpolyols such as the neopentyl polyols; e.g., neopentyl glycol,trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol, trimethylolpropane, pentaerythritol and dipentaerythritol with alkanoic acidscontaining at least about 4 carbon atoms, preferably C₅ to C₃₀ acidssuch as saturated straight chain fatty acids including caprylic acid,capric acids, lauric acid, myristic acid, palmitic acid, stearic acid,arachic acid, and behenic acid, or the corresponding branched chainfatty acids or unsaturated fatty acids such as oleic acid, or mixturesof any of these materials.

Esters should be used in an amount such that the improved wear andcorrosion resistance provided by the lubricating oils of this disclosureare not adversely affected.

Non-conventional or unconventional base stocks and/or base oils includeone or a mixture of base stock(s) and/or base oil(s) derived from: (1)one or more Gas-to-Liquids (GTL) materials, as well as (2) hydrodewaxed,or hydroisomerized/cat (and/or solvent) dewaxed base stock(s) and/orbase oils derived from synthetic wax, natural wax or waxy feeds, mineraland/or non-mineral oil waxy feed stocks such as gas oils, slack waxes(derived from the solvent dewaxing of natural oils, mineral oils orsynthetic oils; e.g., Fischer-Tropsch feed stocks), natural waxes, andwaxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxyraffinate, hydrocrackate, thermal crackates, foots oil or other mineral,mineral oil, or even non-petroleum oil derived waxy materials such aswaxy materials recovered from coal liquefaction or shale oil, linear orbranched hydrocarbyl compounds with carbon number of about 20 orgreater, preferably about 30 or greater and mixtures of such base stocksand/or base oils.

GTL materials are materials that are derived via one or more synthesis,combination, transformation, rearrangement, and/ordegradation/deconstructive processes from gaseous carbon-containingcompounds, hydrogen-containing compounds and/or elements as feed stockssuch as hydrogen, carbon dioxide, carbon monoxide, water, methane,ethane, ethylene, acetylene, propane, propylene, propyne, butane,butylenes, and butynes. GTL base stocks and/or base oils are GTLmaterials of lubricating viscosity that are generally derived fromhydrocarbons; for example, waxy synthesized hydrocarbons, that arethemselves derived from simpler gaseous carbon-containing compounds,hydrogen-containing compounds and/or elements as feed stocks. GTL basestock(s) and/or base oil(s) include oils boiling in the lube oil boilingrange (1) separated/fractionated from synthesized GTL materials such as,for example, by distillation and subsequently subjected to a final waxprocessing step which involves either or both of a catalytic dewaxingprocess, or a solvent dewaxing process, to produce lube oils ofreduced/low pour point; (2) synthesized wax isomerates, comprising, forexample, hydrodewaxed or hydroisomerized cat and/or solvent dewaxedsynthesized wax or waxy hydrocarbons; (3) hydrodewaxed orhydroisomerized cat and/or solvent dewaxed Fischer-Tropsch (F-T)material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possibleanalogous oxygenates); preferably hydrodewaxed orhydroisomerized/followed by cat and/or solvent dewaxing dewaxed F-T waxyhydrocarbons, or hydrodewaxed or hydroisomerized/followed by cat (orsolvent) dewaxing dewaxed. F-T waxes, or mixtures thereof.

GTL base stock(s) and/or base oil(s) derived from GTL materials,especially, hydrodewaxed or hydroisomerized/followed by cat and/orsolvent dewaxed wax or waxy feed, preferably F-T material derived basestock(s) and/or base oil(s), are characterized typically as havingkinematic viscosities at 100° C. of from about 2 mm²/s to about 50 mm²/s(ASTM D445). They are further characterized typically as having pourpoints of −5° C. to about −40° C. or lower (ASTM D97). They are alsocharacterized typically as having viscosity indices of about 80 to about140 or greater (ASTM D2270).

In addition, the GTL base stock(s) and/or base oil(s) are typicallyhighly paraffinic (>90% saturates), and may contain mixtures ofmonocycloparaffins and multicycloparaffins in combination withnon-cyclic isoparaffins. The ratio of the naphthenic (i.e.,cycloparaffin) content in such combinations varies with the catalyst andtemperature used. Further, GTL base stock(s) and/or base oil(s)typically have very low sulfur and nitrogen content, generallycontaining less than about 10 ppm, and more typically less than about 5ppm of each of these elements. The sulfur and nitrogen content of GTLbase stock(s) and/or base oil(s) obtained from F-T material, especiallyF-T wax, is essentially nil. In addition, the absence of phosphorous andaromatics make this materially especially suitable for the formulationof low SAP products.

The term GTL base stock and/or base oil and/or wax isomerate base stockand/or base oil is to be understood as embracing individual fractions ofsuch materials of wide viscosity range as recovered in the productionprocess, mixtures of two or more of such fractions, as well as mixturesof one or two or more low viscosity fractions with one, two or morehigher viscosity fractions to produce a blend wherein the blend exhibitsa target kinematic viscosity.

The GTL material, from which the GTL base stock(s) and/or base oil(s)is/are derived is preferably an F-T material (i.e., hydrocarbons, waxyhydrocarbons, wax).

Base oils for use in the formulated lubricating oils useful in thepresent disclosure are any of the variety of oils corresponding to APIGroup I, Group II, Group III, Group IV, Group V and Group VI oils andmixtures thereof, preferably API Group II, Group III, Group IV, Group Vand Group VI oils and mixtures thereof, more preferably the Group III toGroup VI base oils due to their exceptional volatility, stability,viscometric and cleanliness features. Minor quantities of Group I stock,such as the amount used to dilute additives for blending into formulatedlube oil products, can be tolerated but should be kept to a minimum,i.e. amounts only associated with their use as diluent/carrier oil foradditives used on an “as received” basis. Even in regard to the Group IIstocks, it is preferred that the Group II stock be in the higher qualityrange associated with that stock, i.e. a Group II stock having aviscosity index in the range 100<VI<120.

In addition, the GTL base stock(s) and/or base oil(s) are typicallyhighly paraffinic (>90% saturates), and may contain mixtures ofmonocycloparaffins and multicycloparaffins in combination withnon-cyclic isoparaffins. The ratio of the naphthenic (i.e.,cycloparaffin) content in such combinations varies with the catalyst andtemperature used. Further, GTL base stock(s) and/or base oil(s) andhydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed basestock(s) and/or base oil(s) typically have very low sulfur and nitrogencontent, generally containing less than about 10 ppm, and more typicallyless than about 5 ppm of each of these elements. The sulfur and nitrogencontent of GTL base stock(s) and/or base oil(s) obtained from F-Tmaterial, especially F-T wax, is essentially nil. In addition, theabsence of phosphorous and aromatics make this material especiallysuitable for the formulation of low sulfur, sulfated ash, and phosphorus(low SAP) products.

The base stock component of the present lubricating oils will typicallybe from 50 to 99 weight percent of the total composition (allproportions and percentages set out in this specification are by weightunless the contrary is stated) and more usually in the range of 80 to 99weight percent.

Glycol Ether Substituted Aryl Compound Base Stock and Cobase StockComponents

Glycol ether substituted aryl compound base stock and cobase stockcomponents useful in this disclosure include, for example, compositionscontaining one or more compounds represented by the formulaR₁—O—R₂wherein R₁ is a substituted or unsubstituted aryl or polyaryl grouphaving from about 4 to about 40 carbon atoms, and R₂ is the residue of asubstituted or unsubstituted glycol ether having from about 4 to about40 carbon atoms. The composition has a viscosity (Kv₁₀₀) from about 1 toabout 10 at 100° C. as determined by ASTM D-445, a viscosity index (VI)from about −100 to about 300 as determined by ASTM D-2270, and a Noackvolatility of no greater than 50 percent as determined by ASTM D-5800.

Preferred glycol ether substituted aryl compound base stock and cobasestock components include those in which R₁ is substituted orunsubstituted phenyl, benzyl, naphthyl, or diphenyl (e.g., diphenylamine or diphenyl ether), and R₂ is the residue of a substituted orunsubstituted glycol ether (C₄-C₄₀).

Preferred glycol ether substituted aryl compound base stock and cobasestock components have a viscosity (Kv₁₀₀) from about 1 to about 8, morepreferably from about 2 to about 6, at 100° C. as determined by ASTMD-445, a viscosity index (VI) from about −100 to about 300, morepreferably from about 0 to about 150, even more preferably from about 25to about 100, as determined by ASTM D-2270, and a Noack volatility of nogreater than 75 percent, more preferably no greater than 50 percent,even more preferably no greater than 15 percent, as determined by ASTMD-5800.

Illustrative glycol ether substituted aryl compound base stock andcobase stock components useful in the present disclosure comprise one ormore compounds represented by the formulae

wherein R is a substituted or unsubstituted alkyl group having fromabout 4 to about 40 carbon atoms; and n is a value from about 1 to about12;

wherein R is a substituted or unsubstituted alkyl group having fromabout 4 to about 40 carbon atoms, n is a value from about 1 to about 12;and X is CH₂, O, NR′ or S, wherein R′ is hydrogen or an alkyl grouphaving from 1 to about 4 carbon atoms; and

wherein R is a substituted or unsubstituted alkyl group having fromabout 4 to about 40 carbon atoms; and n is a value from about 1 to about12.

Illustrative glycol ether substituted aryl compound base stock andcobase stock components useful in the present disclosure include, forexample, 1-((2-(2-(hexyloxy)ethoxy)ethoxy)naphthalene,

-   2-(2-(2-(dodecyloxy)ethoxy)ethoxy)benzene,-   (2-(2-hexyloxy)ethoxy)ethoxy)benzene,    1-(2-(2-(hexyloxy)ethoxy)ethoxy)-4-methylbenzene,    4-(2-(2-(hexyloxy)ethoxy)ethoxy)-1,2-dimethylbenzene,-   4-(2-(2-(hexyloxy)ethoxy)ethoxy)-N-phenylaniline,-   1-(2-(2-(hexyloxy)ethoxy)ethoxy)-4-phenoxybenzene,-   1-(2-(2-butoxyethoxy)ethoxy)naphthalene,-   3-(2-ethoxyethoxyethoxy)-2,6-diphenylmethane, and the like.

Illustrative glycol ether substituted aryl compound base stock andcobase stock components useful in the present disclosure include, forexample, the product of reacting a substituted or unsubstituted arylhalide with a substituted or unsubstituted glycol ether, optionally inthe presence of a catalyst, under reaction conditions sufficient toproduce the one or more glycol ether substituted aryl compounds.

Illustrative aryl halides useful in the process of this disclosureinclude, for example,

-   1-iodonaphthalene, iodobenzene, 1-iodo-4-methylbenzene, 4-iodo,    1-2-dimethylbenzene, 4-bromodiphenylamine, 4-bromodiphenylether,-   3-bromodiphenylamine, 2-iodotoluene, 3-iodotoluene,    1-bromo-2,3,-dimethylbenzene, 1-bromo-2,4,-dimethylbenzene,    1-bromo-2-ethylbenzene,-   1-bromo-4-ethylbenzene, 2-bromo-1,3-dimethylbenzene,    2-bromo-1,4-dimethylbenzene, 2-bromo-1,2 dimethylbenzene,    1-bromo-2-ethoxybenzene,-   1-iodo-3,4-dimethylbenzene, 1-iodo-3,5-dimethylbenzene,    2-iodo-1,3-dimethylbenzene, 7-bromo-1H-indene,    1-bromo-3-isopropylbenzene, 1-bromo-4-isopropylbenzene,    1-iodo-4-isopropylbenzene, 2-iodocumene,    5-iodo-1,2,3,-trimethylbenzene, 1-bromo-3-(trimethylsiliyl)benzene,    1-bromo-4-(trimethylsiliyl)benzene, 2-bromonapthalene,    2-iodonapthalene, 1-bromo-4-tert.butylbenzene,    1-iodo-4-tertbutylbenzene, 1-bromo-4-methylnapthalene,-   1-bromo-2-methylnapthalene, 2-bromobiphenyl, 4-bromobiphenyl,-   3-bromobiphenyl, 3-bromophenathrene, 2-bromofluorene,    9-bromofluorene,-   9-bromoanthracene, 9-bromophenathrene, 9-iodophenathrene,    1-bromo-3,5-tert-butylbenzene, 1-bromopyrene, and the like.

Illustrative glycol ethers useful in the process of this disclosureinclude, for example, di(ethylene glycol)butyl ether, di(ethyleneglycol) hexyl ether, di(ethylene glycol) dodecyl ether, and the like.

Other illustrative glycol ethers include, for example, di(ethyleneglycol) monohexyl ether, tri(ethylene glycol) monomethyl ether,tri(propylene glycol) monomethyl ether, tri(ethylene glycol) monoethylether, tri(ethylene glycol) monobutyl ether, di(ethylene glycol)monoethyl ether, di(ethylene glycol) monobutyl ether, tri(propyleneglycol) monopropyl ether, tri(propylene glycol) monobutyl ether,poly(ethylene glycol) dodecyl ether (Brij 30), ethylene glycolmono-2-ethylhexyl ether, and the like. By changing the glycol ethermolecules, the fluid can be synthesized with various polarity.

Glycol ethers, with both an ether and alcohol functional groups in thesame molecule, are one of the most versatile classes of organicsolvents. The Dow Chemical Company manufactures glycol ethers in largequantities. DOW glycol ether products are produced through continuousprocesses of selectively reacting an alcohol (ethanol, butanol, hexanol)with ethylene oxide. Diethylene glycol monohexyl ether[(C₆H₁₃(OCH₂CH₂)₂OH, Hexyl CARBITOL Solvent) displays a stronghydrocarbon-type solvency.

Additionally, illustrative glycol ether substituted aryl compound basestock and cobase stock components useful in the present disclosureinclude, for example, the product of reacting a substituted orunsubstituted aryl alcohol with a substituted or unsubstituted glycolether halide, optionally in the presence of a catalyst, under reactionconditions sufficient to produce said one or more glycol ethersubstituted aryl compounds.

Illustrative aryl alcohols useful in the process of this disclosureinclude, for example, 4-benzylphenol, 5,6,7,8,-tetrahydro-1-napthol,5,6,7,8,-tetrahydro-2-napthol, 2-napthol, 1-napthol, 2-benzylphenol,4-phenoxyphenol, 2-methyl-1-napthol, 6-methoxy-2-napthol,3-methoxy-2-napthol, 7-methoxy-2-napthol, 3-phenylphenol,2-phenylphenol, 4-phenylphenol, and the like.

Illustrative glycol ether halides useful in the process of thisdisclosure include, for example, 2-(2-ethoxyethoxy)ethyl bromide, andthe like. By changing the glycol ether halide molecules, the fluid canbe synthesized with various polarity.

The glycol ether substituted aryl compound cobase stock component ispreferably present in an amount sufficient for providing oxidativestability in the lubricating oil. The glycol ether substituted arylcompound cobase stock component is present in the lubricating oils ofthis disclosure in an amount from about 1 to about 50 weight percent,preferably from about 5 to about 30 weight percent, and more preferablyfrom about 10 to about 20 weight percent.

The glycol ether substituted aryl compound base stock component of thepresent lubricating oils will typically be from 20 to 80 weight percentor from 50 to 99 weight percent of the total composition (allproportions and percentages set out in this specification are by weightunless the contrary is stated) and more usually in the range of 80 to 99weight percent.

Other Additives

The formulated lubricating oil useful in the present disclosure mayadditionally contain one or more of the other commonly used lubricatingoil performance additives including but not limited to dispersants,other detergents, corrosion inhibitors, rust inhibitors, metaldeactivators, other anti-wear agents and/or extreme pressure additives,anti-seizure agents, wax modifiers, viscosity index improvers, viscositymodifiers, fluid-loss additives, seal compatibility agents, otherfriction modifiers, lubricity agents, anti-staining agents, chromophoricagents, defoamants, demulsifiers, emulsifiers, densifiers, wettingagents, gelling agents, tackiness agents, colorants, and others. For areview of many commonly used additives, see Klamann in Lubricants andRelated Products, Verlag Chemie, Deerfield Beach, Fla., ISBN0-89573-177-0. Reference is also made to “Lubricant Additives Chemistryand Applications” edited by Leslie R. Rudnick, Marcel Dekker, Inc. NewYork, 2003 ISBN: 0-8247-0857-1.

The types and quantities of performance additives used in combinationwith the instant disclosure in lubricant compositions are not limited bythe examples shown herein as illustrations.

Viscosity Improvers

Viscosity improvers (also known as Viscosity Index modifiers, and VIimprovers) increase the viscosity of the oil composition at elevatedtemperatures which increases film thickness, while having limited effecton viscosity at low temperatures.

Suitable viscosity improvers include high molecular weight hydrocarbons,polyesters and viscosity index improver dispersants that function asboth a viscosity index improver and a dispersant. Typical molecularweights of these polymers are between about 10,000 to 1,000,000, moretypically about 20,000 to 500,000, and even more typically between about50,000 and 200,000.

Examples of suitable viscosity improvers are polymers and copolymers ofmethacrylate, butadiene, olefins, or alkylated styrenes. Polyisobutyleneis a commonly used viscosity index improver. Another suitable viscosityindex improver is polymethacrylate (copolymers of various chain lengthalkyl methacrylates, for example), some formulations of which also serveas pour point depressants. Other suitable viscosity index improversinclude copolymers of ethylene and propylene, hydrogenated blockcopolymers of styrene and isoprene, and polyacrylates (copolymers ofvarious chain length acrylates, for example). Specific examples includestyrene-isoprene or styrene-butadiene based polymers of 50,000 to200,000 molecular weight.

The amount of viscosity modifier may range from zero to 8 wt %,preferably zero to 4 wt %, more preferably zero to 2 wt % based onactive ingredient and depending on the specific viscosity modifier used.

Antioxidants

Typical antioxidant include phenolic antioxidants, aminic antioxidantsand oil-soluble copper complexes.

The phenolic antioxidants include sulfurized and non-sulfurized phenolicantioxidants. The terms “phenolic type” or “phenolic antioxidant” usedherein includes compounds having one or more than one hydroxyl groupbound to an aromatic ring which may itself be mononuclear, e.g., benzyl,or poly-nuclear, e.g., naphthyl and spiro aromatic compounds. Thus“phenol type” includes phenol per se, catechol, resorcinol,hydroquinone, naphthol, etc., as well as alkyl or alkenyl and sulfurizedalkyl or alkenyl derivatives thereof, and bisphenol type compoundsincluding such bi-phenol compounds linked by alkylene bridges sulfuricbridges or oxygen bridges. Alkyl phenols include mono- and poly-alkyl oralkenyl phenols, the alkyl or alkenyl group containing from about 3-100carbons, preferably 4 to 50 carbons and sulfurized derivatives thereof,the number of alkyl or alkenyl groups present in the aromatic ringranging from 1 to up to the available unsatisfied valences of thearomatic ring remaining after counting the number of hydroxyl groupsbound to the aromatic ring.

Generally, therefore, the phenolic anti-oxidant may be represented bythe general formula:(R)_(x)—Ar—(OH)_(y)where Ar is selected from the group consisting of:

wherein R is a C₃-C₁₀₀ alkyl or alkenyl group, a sulfur substitutedalkyl or alkenyl group, preferably a C₄-C₅₀ alkyl or alkenyl group orsulfur substituted alkyl or alkenyl group, more preferably C₃-C₁₀₀ alkylor sulfur substituted alkyl group, most preferably a C₄-C₅₀ alkyl group,R^(G) is a C₁-C₁₀₀ alkylene or sulfur substituted alkylene group,preferably a C₂-C₅₀ alkylene or sulfur substituted alkylene group, morepreferably a C₂-C₂ alkylene or sulfur substituted alkylene group, y isat least 1 to up to the available valences of Ar, x ranges from 0 to upto the available valances of Ar-y, z ranges from 1 to 10, n ranges from0 to 20, and m is 0 to 4 and p is 0 or 1, preferably y ranges from 1 to3, x ranges from 0 to 3, z ranges from 1 to 4 and n ranges from 0 to 5,and p is 0.

Preferred phenolic anti-oxidant compounds are the hindered phenolics andphenolic esters which contain a sterically hindered hydroxyl group, andthese include those derivatives of dihydroxy aryl compounds in which thehydroxyl groups are in the o- or p-position to each other. Typicalphenolic anti-oxidants include the hindered phenols substituted with C₁+alkyl groups and the alkylene coupled derivatives of these hinderedphenols. Examples of phenolic materials of this type 2-t-butyl-4-heptylphenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol;2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol;2-methyl-6-t-butyl-4-heptyl phenol; 2-methyl-6-t-butyl-4-dodecyl phenol;2,6-di-t-butyl-4 methyl phenol; 2,6-di-t-butyl-4-ethyl phenol; and2,6-di-t-butyl 4 alkoxy phenol; and

Phenolic type anti-oxidants are well known in the lubricating industryand commercial examples such as Ethanox® 4710, Irganox® 1076, Irganox®L1035, Irganox® 1010, Irganox® L109, Irganox® L118, Irganox® L135 andthe like are familiar to those skilled in the art. The above ispresented only by way of exemplification, not limitation on the type ofphenolic anti-oxidants which can be used.

The phenolic anti-oxidant can be employed in an amount in the range ofabout 0.1 to 3 wt %, preferably about 1 to 3 wt %, more preferably 1.5to 3 wt % on an active ingredient basis.

Aromatic amine anti-oxidants include phenyl-α-naphthyl amine which isdescribed by the following molecular structure:

wherein R^(z) is hydrogen or a C₁ to C₁₄ linear or C₃ to C₁₄ branchedalkyl group, preferably C₁ to C₁₀ linear or C₃ to C₁₀ branched alkylgroup, more preferably linear or branched C₆ to C₈ and n is an integerranging from 1 to 5 preferably 1. A particular example is Irganox L06.

Other aromatic amine anti-oxidants include other alkylated andnon-alkylated aromatic amines such as aromatic monoamines of the formulaR⁸R⁹R¹⁰N where R⁸ is an aliphatic, aromatic or substituted aromaticgroup, R⁹ is an aromatic or a substituted aromatic group, and R¹⁰ is H,alkyl, aryl or R¹¹S(O)_(x)R¹² where R¹¹ is an alkylene, alkenylene, oraralkylene group, R¹² is a higher alkyl group, or an alkenyl, aryl, oralkaryl group, and x is 0, 1 or 2. The aliphatic group R⁸ may containfrom 1 to about 20 carbon atoms, and preferably contains from about 6 to12 carbon atoms. The aliphatic group is a saturated aliphatic group.Preferably, both R⁸ and R⁹ are aromatic or substituted aromatic groups,and the aromatic group may be a fused ring aromatic group such asnaphthyl. Aromatic groups R⁸ and R⁹ may be joined together with othergroups such as S.

Typical aromatic amines anti-oxidants have alkyl substituent groups ofat least about 6 carbon atoms. Examples of aliphatic groups includehexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groupswill not contain more than about 14 carbon atoms. The general types ofsuch other additional amine anti-oxidants which may be present includediphenylamines, phenothiazines, imidodibenzyls and diphenyl phenylenediamines. Mixtures of two or more of such other additional aromaticamines may also be present. Polymeric amine antioxidants can also beused.

Another class of anti-oxidant used in lubricating oil compositions andwhich may also be present are oil-soluble copper compounds. Anyoil-soluble suitable copper compound may be blended into the lubricatingoil. Examples of suitable copper antioxidants include copperdihydrocarbyl thio- or dithio-phosphates and copper salts of carboxylicacid (naturally occurring or synthetic). Other suitable copper saltsinclude copper dithiacarbamates, sulphonates, phenates, andacetylacetonates. Basic, neutral, or acidic copper Cu(I) and or Cu(II)salts derived from alkenyl succinic acids or anhydrides are known to beparticularly useful.

Such antioxidants may be used individually or as mixtures of one or moretypes of anti-oxidants, the total amount employed being an amount ofabout 0.50 to 5 wt %, preferably about 0.75 to 3 wt % (on an as-receivedbasis).

Detergents

In addition to the alkali or alkaline earth metal salicylate detergentwhich is an essential component in the present disclosure, otherdetergents may also be present. While such other detergents can bepresent, it is preferred that the amount employed be such as to notinterfere with the synergistic effect attributable to the presence ofthe salicylate. Therefore, most preferably such other detergents are notemployed.

If such additional detergents are present, they can include alkali andalkaline earth metal phenates, sulfonates, carboxylates, phosphonatesand mixtures thereof. These supplemental detergents can have total basenumber (TBN) ranging from neutral to highly overbased, i.e. TBN of 0 toover 500, preferably 2 to 400, more preferably 5 to 300, and they can bepresent either individually or in combination with each other in anamount in the range of from 0 to 10 wt %, preferably 0.5 to 5 wt %(active ingredient) based on the total weight of the formulatedlubricating oil. As previously stated, however, it is preferred thatsuch other detergent not be present in the formulation.

Such additional other detergents include by way of example and notlimitation calcium phenates, calcium sulfonates, magnesium phenates,magnesium sulfonates and other related components (including borateddetergents).

Dispersants

During engine operation, oil-insoluble oxidation byproducts areproduced. Dispersants help keep these byproducts in solution, thusdiminishing their deposition on metal surfaces. Dispersants may beashless or ash-forming in nature. Preferably, the dispersant is ashless.So called ashless dispersants are organic materials that formsubstantially no ash upon combustion. For example, non-metal-containingor borated metal-free dispersants are considered ashless. In contrast,metal-containing detergents discussed above form ash upon combustion.

Suitable dispersants typically contain a polar group attached to arelatively high molecular weight hydrocarbon chain. The polar grouptypically contains at least one element of nitrogen, oxygen, orphosphorus. Typical hydrocarbon chains contain 50 to 400 carbon atoms.

A particularly useful class of dispersants are the alkenylsuccinicderivatives, typically produced by the reaction of a long chainsubstituted alkenyl succinic compound, usually a substituted succinicanhydride, with a polyhydroxy or polyamino compound. The long chaingroup constituting the oleophilic portion of the molecule which conferssolubility in the oil, is normally a polyisobutylene group. Manyexamples of this type of dispersant are well known commercially and inthe literature. Exemplary patents describing such dispersants are U.S.Pat. Nos. 3,172,892; 3,219,666; 3,316,177 and 4,234,435. Other types ofdispersants are described in U.S. Pat. No. 3,036,003; and 5,705,458.

Hydrocarbyl-substituted succinic acid compounds are popular dispersants.In particular, succinimide, succinate esters, or succinate ester amidesprepared by the reaction of a hydrocarbon-substituted succinic acidcompound preferably having at least 50 carbon atoms in the hydrocarbonsubstituent, with at least one equivalent of an alkylene amine areparticularly useful.

Succinimides are formed by the condensation reaction between alkenylsuccinic anhydrides and amines. Molar ratios can vary depending on theamine or polyamine. For example, the molar ratio of alkenyl succinicanhydride to TEPA can vary from about 1:1 to about 5:1.

Succinate esters are formed by the condensation reaction between alkenylsuccinic anhydrides and alcohols or polyols. Molar ratios can varydepending on the alcohol or polyol used. For example, the condensationproduct of an alkenyl succinic anhydride and pentaerythritol is a usefuldispersant.

Succinate ester amides are formed by condensation reaction betweenalkenyl succinic anhydrides and alkanol amines. For example, suitablealkanol amines include ethoxylated polyalkylpolyamines, propoxylatedpolyalkylpolyamines and polyalkenylpolyamines such as polyethylenepolyamines. One example is propoxylated hexamethylenediamine.

The molecular weight of the alkenyl succinic anhydrides will typicallyrange between 800 and 2,500. The above products can be post-reacted withvarious reagents such as sulfur, oxygen, formaldehyde, carboxylic acidssuch as oleic acid, and boron compounds such as borate esters or highlyborated dispersants. The dispersants can be borated with from about 0.1to about 5 moles of boron per mole of dispersant reaction product.

Mannich base dispersants are made from the reaction of alkylphenols,formaldehyde, and amines. Process aids and catalysts, such as oleic acidand sulfonic acids, can also be part of the reaction mixture. Molecularweights of the alkylphenols range from 800 to 2,500.

Typical high molecular weight aliphatic acid modified Mannichcondensation products can be prepared from high molecular weightalkyl-substituted hydroxyaromatics or HN(R)₂ group-containing reactants.

Examples of high molecular weight alkyl-substituted hydroxyaromaticcompounds are polypropylphenol, polybutylphenol, and otherpolyalkylphenols. These polyalkylphenols can be obtained by thealkylation, in the presence of an alkylating catalyst, such as BF₃, ofphenol with high molecular weight polypropylene, polybutylene, and otherpolyalkylene compounds to give alkyl substituents on the benzene ring ofphenol having an average 600-100,000 molecular weight.

Examples of HN(R)₂ group-containing reactants are alkylene polyamines,principally polyethylene polyamines. Other representative organiccompounds containing at least one HN(R)₂ group suitable for use in thepreparation of Mannich condensation products are well known and includethe mono- and di-amino alkanes and their substituted analogs, e.g.,ethylamine and diethanol amine; aromatic diamines, e.g., phenylenediamine, diamino naphthalenes; heterocyclic amines, e.g., morpholine,pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; melamineand their substituted analogs.

Examples of alkylene polyamine reactants include ethylenediamine,diethylene triamine, triethylene tetraamine, tetraethylene pentaamine,pentaethylene hexamine, hexaethylene heptaamine, heptaethyleneoctaamine, octaethylene nonaamine, nonaethylene decamine, anddecaethylene undecamine and mixture of such amines having nitrogencontents corresponding to the alkylene polyamines, in the formulaH₂N—(Z—NH—)_(n)H, mentioned before, Z is a divalent ethylene and n is 1to 10 of the foregoing formula. Corresponding propylene polyamines suchas propylene diamine and di-, tri-, tetra-, pentapropylene tri-, tetra-,penta- and hexaamines are also suitable reactants. The alkylenepolyamines are usually obtained by the reaction of ammonia and dihaloalkanes, such as dichloro alkanes. Thus the alkylene polyamines obtainedfrom the reaction of 2 to 11 moles of ammonia with 1 to 10 moles ofdichloroalkanes having 2 to 6 carbon atoms and the chlorines ondifferent carbons are suitable alkylene polyamine reactants.

Aldehyde reactants useful in the preparation of the high molecularproducts useful in this disclosure include the aliphatic aldehydes suchas formaldehyde (also as paraformaldehyde and formalin), acetaldehydeand aldol (β-hydroxybutyraldehyde). Formaldehyde or aformaldehyde-yielding reactant is preferred.

Preferred dispersants include borated and non-borated succinimides,including those derivatives from mono-succinimides, bis-succinimides,and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbylsuccinimide is derived from a hydrocarbylene group such aspolyisobutylene having a Mn of from about 500 to about 5000 or a mixtureof such hydrocarbylene groups. Other preferred dispersants includesuccinic acid-esters and amides, alkylphenol-polyamine-coupled Mannichadducts, their capped derivatives, and other related components. Suchadditives may be used in an amount of about 0.1 to 20 wt %, preferablyabout 0.1 to 8 wt %, more preferably about 1 to 6 wt % (on anas-received basis) based on the weight of the total lubricant.

Pour Point Depressants

Conventional pour point depressants (also known as lube oil flowimprovers) may also be present. Pour point depressant may be added tolower the minimum temperature at which the fluid will flow or can bepoured. Examples of suitable pour point depressants include alkylatednaphthalenes polymethacrylates, polyacrylates, polyarylamides,condensation products of haloparaffin waxes and aromatic compounds,vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinylesters of fatty acids and allyl vinyl ethers. Such additives may be usedin amount of about 0.0 to 0.5 wt %, preferably about 0 to 0.3 wt %, morepreferably about 0.001 to 0.1 wt % on an as-received basis.

Corrosion Inhibitors/Metal Deactivators

Corrosion inhibitors are used to reduce the degradation of metallicparts that are in contact with the lubricating oil composition. Suitablecorrosion inhibitors include aryl thiazines, alkyl substituteddimercapto thiodiazoles thiadiazoles and mixtures thereof. Suchadditives may be used in an amount of about 0.01 to 5 wt %, preferablyabout 0.01 to 1.5 wt/o, more preferably about 0.01 to 0.2 wt %, stillmore preferably about 0.01 to 0.1 wt % (on an as-received basis) basedon the total weight of the lubricating oil composition.

Seal Compatibility Additives

Seal compatibility agents help to swell elastomeric seals by causing achemical reaction in the fluid or physical change in the elastomer.Suitable seal compatibility agents for lubricating oils include organicphosphates, aromatic esters, aromatic hydrocarbons, esters (butylbenzylphthalate, for example), and polybutenyl succinic anhydride andsulfolane-type seal swell agents such as Lubrizol 730-type seal swelladditives. Such additives may be used in an amount of about 0.01 to 3 wt%, preferably about 0.01 to 2 wt % on an as-received basis.

Anti-Foam Agents

Anti-foam agents may advantageously be added to lubricant compositions.These agents retard the formation of stable foams. Silicones and organicpolymers are typical anti-foam agents. For example, polysiloxanes, suchas silicon oil or polydimethyl siloxane, provide antifoam properties.Anti-foam agents are commercially available and may be used inconventional minor amounts along with other additives such asdemulsifiers; usually the amount of these additives combined is lessthan 1 percent, preferably 0.001 to about 0.5 wt %, more preferablyabout 0.001 to about 0.2 wt %, still more preferably about 0.0001 to0.15 wt/t % (on an as-received basis) based on the total weight of thelubricating oil composition.

Inhibitors and Antirust Additives

Anti-rust additives (or corrosion inhibitors) are additives that protectlubricated metal surfaces against chemical attack by water or othercontaminants. One type of anti-rust additive is a polar compound thatwets the metal surface preferentially, protecting it with a film of oil.Another type of anti-rust additive absorbs water by incorporating it ina water-in-oil emulsion so that only the oil touches the surface. Yetanother type of anti-rust additive chemically adheres to the metal toproduce a non-reactive surface. Examples of suitable additives includezinc dithiophosphates, metal phenolates, basic metal sulfonates, fattyacids and amines. Such additives may be used in an amount of about 0.01to 5 wt %, preferably about 0.01 to 1.5 wt % on an as-received basis.

In addition to the ZDDP anti-wear additives which are essentialcomponents of the present disclosure, other anti-wear additives can bepresent, including zinc dithiocarbamates, molybdenumdialkyldithiophosphates, molybdenum dithiocarbamates, other organomolybdenum-nitrogen complexes, sulfurized olefins, etc.

The term “organo molybdenum-nitrogen complexes” embraces the organomolybdenum-nitrogen complexes described in U.S. Pat. No. 4,889,647. Thecomplexes are reaction products of a fatty oil, dithanolamine and amolybdenum source. Specific chemical structures have not been assignedto the complexes. U.S. Pat. No. 4,889,647 reports an infrared spectrumfor a typical reaction product of that disclosure; the spectrumidentifies an ester carbonyl band at 1740 cm⁻¹ and an amide carbonylband at 1620 cm⁻¹. The fatty oils are glyceryl esters of higher fattyacids containing at least 12 carbon atoms up to 22 carbon atoms or more.The molybdenum source is an oxygen-containing compound such as ammoniummolybdates, molybdenum oxides and mixtures.

Other organo molybdenum complexes which can be used in the presentdisclosure are tri-nuclear molybdenum-sulfur compounds described in EP 1040 115 and WO 99/31113 and the molybdenum complexes described in U.S.Pat. No. 4,978,464.

In the above detailed description, the specific embodiments of thisdisclosure have been described in connection with its preferredembodiments. However, to the extent that the above description isspecific to a particular embodiment or a particular use of thisdisclosure, this is intended to be illustrative only and merely providesa concise description of the exemplary embodiments. Accordingly, thedisclosure is not limited to the specific embodiments described above,but rather, the disclosure includes all alternatives, modifications, andequivalents falling within the true scope of the appended claims.Various modifications and variations of this disclosure will be obviousto a worker skilled in the art and it is to be understood that suchmodifications and variations are to be included within the purview ofthis application and the spirit and scope of the claims.

EXAMPLES Example 1 Synthesis of1-((2-(2-(hexyloxy)ethoxy)ethoxy)naphthalene

Charged 1-iodonapthalene (5 grams, 19.679 mmol, MW: 254.07), di(ethyleneglycol) hexyl ether (7.50 grams, 39.416 mmol, MW: 190.29), cesiumcarbonate, (9.7 grams, 29.528 mmol, MW: 328.5), 1,10-phenathroline(0.709 grams, 3.94 mmol, MW: 180.21), copper (I) iodide (0.384 grams,1.97 mmol, MW: 195.01) and 50 milliliters of dry xylene in 350milliliter three necked round bottom flask. The reaction mixture washeated with stirring at 140° C. for 24 hours under nitrogen. Theresulting suspension was cooled to room temperature and filtered throughcelite and alumina. The filtrate was concentrated at 180° C. under highvacuum. The residue was purified by flask chromatography on silica gelwith hexane. The final pale yellow product was yielded 4.2 grams (67%).The product ¹³C NMR analysis suggests the formation of naphthyl etherproduct. ¹³C NMR (CDCl₃): 154.70, 134.75, 127.50, 126.46, 125.93,125.31, 122.28, 120.51, 104.98, 71.69, 71.12, 70.28, 69.85, 67.94,31.79, 29.77, 25.92, 22.72, 14.21.

Example 2 Synthesis of 2-(2-(2-(dodecyloxy)ethoxy)ethoxy)benzene

Charged iodobenzene (11.15 grams, 54.654 mmol, MW: 204.01), di(ethyleneglycol) dodecyl ether (10.0 grams, 36.437 mmol, MW: 174.44), cesiumcarbonate (17.96 grams, 54.673 mmol, MW: 328.5), 1,10-phenathroline(1.312 grams, 7.280 mmol, MW: 180.21), copper (I) iodide (0.711 grams,3.645 mmol, MW: 195.01) and 50 milliliters of dry xylene in 350milliliter three necked round bottom flask. The reaction mixture washeated with stirring at 140° C. for 24 hours under nitrogen. Theresulting suspension was cooled to room temperature and filtered throughcelite and alumina. The filtrate was concentrated at 180° C. under highvacuum. The residue was purified by flask chromatography on silica gelwith hexane. The final yellow product was yielded 5.0 grams (39%). Theproduct ¹³C NMR analysis suggests the formation of aryl ether product.¹³C NMR (CDCl₃): 159.03, 129.70, 121.10, 114.78, 71.60, 70.90, 70.15,69.79, 67.33, 31.95, 29.70, 29.70, 29.67, 29.64 29.52, 29.38, 26.13,22.71, 14.14.

Example 3 Synthesis of (2-(2-hexyloxy)ethoxy)ethoxy)benzene

Charged copper (I) iodide (1.91 grams, 0.00098 mol), 1,10-phenathraoline(3.55 grams, 0.0197 mol), cesium carbonate (48 g, 0.1461 mol),iodobenzene (20 grams, 0.0980 mol), di(ethylene glycol) hexyl ether (28grams, 0.1473 mol) and 75 milliliters of dry xylene in 350 milliliterround bottom flask. The reaction mixture was heated with stirring at120° C. for 24 hours under nitrogen. The resulting suspension was cooledto room temperature and filter through celite and alumina. The filtratewas concentrated at high vacuum. The residue was purified by flaskchromatography on silica gel with 1:1 hexane and ethyl acetate. Thefinal light yellow product was yielded 20 grams (77%). The product ¹HNMR analysis suggests the formation of aryl ether product. ¹H NMR(CDCl₃): δ7.27-6.92 (m 5H, Ph), 4.13 (t, 2H, —OCH₂—), 3.87 (t, 2H,—CH₂O), 3.70-3.59 (m, 4H, —OCH₂—CH₂O—), 3.46 (t, 2H), 1.57-1.29 (m, 8H,—CH₂—), 0.88 (t, 3H, —CH₃).

Example 4 Synthesis of 1-(2-(2-(hexyloxy)ethoxy)ethoxy)-4-methylbenzene

Charged iodotoluene (5.0 grams, 22.93 mmol, MW: 218.03), di(ethyleneglycol) monohexylether (8.73 grams, 45.88 mmol, MW: 190.28), cesiumcarbonate, (11.28 grams, 34.34 mmol, MW: 328.5), 1,10-phenathroline(0.825 grams, 4.58 mmol, MW: 180.21), copper (I) iodide (0.447 grams,2.29 mmol, MW: 195.01) and 50 milliliters of dry xylene in 350milliliter three necked round bottom flask. The reaction mixture washeated with stirring at 140° C. for 24 hours under nitrogen. Theresulting suspension was cooled to room temperature and filtered throughcelite and alumina. The low boiling (xylene) component removed by rotaryevaporator and high boiling component by air bath oven at 180° C. underhigh vacuum. The residue was purified by flask chromatography on silicagel with hexane. The final yellow product was yielded 4.0 grams (63%).The product ¹³C NMR analysis suggests the formation of aryl etherproduct. ¹³C NMR (CDCl₃): 156.77, 130.03, 114.72, 71.64, 70.91, 70.15,69.85, 67.51, 31.72, 29.65, 25.82, 22.66, 20.15, 14.07.

Example 5 Synthesis of4-(2-(2-(hexyloxy)ethoxy)ethoxy)-1,2-dimethylbenzene

Charged 1-iodo-3,4-dimethylbenzene (10.0 grams, 43.09 mmol, MW: 232.06),di(ethylene glycol) monohexylether (16.39 grams, 86.18 mmol, MW:190.28), cesium carbonate, (21.23 grams, 64.60 mmol, MW: 328.5),1,10-phenathroline (1.55 grams, 4.58 mmol, MW: 180.21), copper (I)iodide (0.447 grams, 2.29 mmol, MW: 195.01) and 50 milliliters of dryxylene in 350 milliliter three necked round bottom flask. The reactionmixture was heated with stirring at 140° C. for 24 hours under nitrogen.The resulting suspension was cooled to room temperature and filteredthrough celite and alumina. The low boiling (xylene) component removedby rotary evaporator and high boiling component by air bath oven at 180°C. under high vacuum. The residue was purified by flask chromatographyon silica gel with hexane. The final yellow product was yielded 7.6grams (60%). The product ¹³C NMR analysis suggests the formation of arylether product. ¹³C NMR (CDCl₃): 157.42, 137.68, 130.34, 128.57, 116.37,111.50, 71.64, 70.87, 70.15, 69.88, 67.46, 31.75, 29.68, 25.84, 22.66,20.06, 18.79, 14.08.

Example 6 Synthesis of 1-(2-(2-butoxyethoxy)ethoxy)naphthalene

Charged 1-iodonapthalene (10 grams, 39.359 mmol, MW: 254.07),di(ethylene glycol)butyl ether (12.78 grams, 78.70 mmol, MW: 162.23),cesium carbonate, (19.40 grams, 59.10 mmol, MW: 328.5),1,10-phenathroline (1.408 grams, 7.873 mmol, MW: 180.21), copper (I)iodide (0.768 grams, 3.90 mmol, MW: 195.01) and 70 milliliters of dryxylene in 350 milliliter three necked round bottom flask. The reactionmixture was heated with stirring at 145° C. for 26 hours under nitrogen.The resulting suspension was cooled to room temperature and filteredthrough celite. The filtrate was concentrated at 180° C. under highvacuum. The residue was purified by flask chromatography on silica gelwith hexane. The final pale yellow product was yielded 9.0 g (79%). The¹³C NMR analysis of the product suggests the formation of desirednaphthyl fluid. ¹³C NMR (CDCl₃): 154.71, 134.64, 127.51, 126.44, 125.88,125.80, 125.16, 122.26, 120.43, 104.94, 71.32, 71.08, 70.25, 69.85,67.94, 31.81, 19.33, 13.97.

Example 7 Synthesis of 3-(2-ethoxyethoxyethoxy)-2,6-diphenylmethane

A 2-neck round-bottomed flask was charged with acetonitrile (630milliliters) and potassium carbonate (165 grams, 1.194 moles). Themixture was stirred and 4-benzylphenol (76.5 grams, 415 millimoles) wasadded. The mixture was heated to reflux under nitrogen for 3 hours, thenallowed to cool down. 2-(2-Ethoxyethoxy)ethyl bromide (100 grams, 507millimoles) and additional acetonitrile (150 milliliters) were added.The mixture was reheated to reflux and maintained for 48 hours. Afterthe reaction mixture was cooled down, it was filtered and theprecipitate was washed with methylene chloride. The combined filtratewas concentrated and diluted with methylene chloride. The solution waswashed with potassium hydroxide aqueous solution (3 moles/liter),hydrogen chloride solution (3 moles/liter) twice and distilled watersequentially. The organic phase was dried over magnesium sulfate, andevaporated under vacuum to remove the solvent. The crude product waspurified by vacuum distillation using a Kugelrohr apparatus. The finalproduct was determined by ¹H NMR, ¹³C NMR and GC. Yields: 86.4 g (69%).¹H NMR (CDCl₃): δ 7.27-6.83 (m, 9H, Ph), 3.91 (s, 2H, PhCH₂ Ph-), 4.10,3.84, 3.70, 3.61 (t, 2H each, —OCH₂ CH₂ OCH₂ CH₂ OCH₂CH₃), 3.53 (q, 2H,—OCH₂ CH₃), 1.21 (t, 3H, —CH₃). ¹³C NMR (CDCl₃): δ 157.3, 141.7, 133.6,130.0, 128.9, 128.5, 126.1, 114.1 (Ph), 71.0, 70.0, 69.9, 67.6, 66.8(—OCH₂ CH₂OCH₂ CH₂OCH₂CH₃), 41.2 (PhCH₂Ph-), 15.3 (—CH₃).

Example 8 Lube Properties

The lube properties of the products of Examples 1-7 were evaluated andthe data are shown below. The kinematic viscosity (Kv) of the liquidproduct was measured using ASTM standards D-445 and reported attemperatures of 100° C. (Kv at 100° C.) or 40° C. (Kv at 40° C.). Theviscosity index (VI) was measured according to ASTM standard D-2270using the measured kinematic viscosities for each product. The productvolatility was measured using thermogravimetric analysis (TGA) basedNoack. Noack volatility was determined by ASTM D-5800. These fluids wereevaluated as Group V base stocks and the results are shown in FIG. 1.

By changing the glycol ether portion, molecules with varying polaritycan be synthesized. These molecules can be used as low viscosity basestocks or can be used as cobase stocks along with mPAO, PAO, GroupI-III+, GTL. This fuel economy enabling base stock provide opportunityfor step-out lubricants with distinguishable and marketable features.Besides base stocks there molecules can also be used as a non-phthalate,non-ester but ether based PVC plasticizers.

The fluids of Examples 1-7 have improved viscosity-volatilitycharacteristics compared to hydrocarbons fluids such as PAO4, mPAO3.4,PAO2, and mPAO2, as shown in FIG. 2.

PCT and EP Clauses:

1. A composition comprising one or more compounds represented by theformulaR₁—O—R₂wherein R₁ is a substituted or unsubstituted aryl or polyaryl grouphaving from 4 to 40 carbon atoms, and R₂ is the residue of a substitutedor unsubstituted glycol ether having from 4 to 40 carbon atoms; whereinsaid composition has a viscosity (Kv₁₀₀) from 1 to 10 cSt at 100° C. asdetermined by ASTM D-445, a viscosity index (VI) from −100 to 300 asdetermined by ASTM D-2270, and a Noack volatility of no greater than 50percent as determined by ASTM D-5800.

2. The composition of clause 1 wherein R₁ is substituted orunsubstituted phenyl, benzyl, naphthyl, or diphenyl, and R₂ is theresidue of a substituted or unsubstituted glycol ether (C₄-C₄₀).

3. The composition of clauses 1 and 2 which is selected from one or morecompounds represented by the formulae

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms; and n is a value from 1 to 12;

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms, n is a value from 1 to 12; and X is CH₂, O, NR′ or S,wherein R′ is hydrogen or an alkyl group having from 1 to 4 carbonatoms; and

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms; and n is a value from 1 to 12.

4. The composition of clauses 1-3 which is selected from1-((2-(2-(hexyloxy)ethoxy)ethoxy)naphthalene,

-   2-(2-(2-(dodecyloxy)ethoxy)ethoxy)benzene,-   (2-(2-hexyloxy)ethoxy)ethoxy)benzene,    1-(2-(2-(hexyloxy)ethoxy)ethoxy)-4-methylbenzene,    4-(2-(2-(hexyloxy)ethoxy)ethoxy)-1,2-dimethylbenzene,-   4-(2-(2-(hexyloxy)ethoxy)ethoxy)-N-phenylaniline,-   1-(2-(2-(hexyloxy)ethoxy)ethoxy)-4-phenoxybenzene,-   1-(2-(2-butoxyethoxy)ethoxy)naphthalene, and    3-(2-ethoxyethoxyethoxy)-2,6-diphenylmethane.

5. A composition comprising one or more glycol ether substituted arylcompounds represented by the formulaR₁—O—R₂wherein R₁ is a substituted or unsubstituted aryl or polyaryl grouphaving from 4 to 40 carbon atoms, and R₂ is the residue of a substitutedor unsubstituted glycol ether having from 4 to 40 carbon atoms; whereinsaid composition has a viscosity (Kv₁₀₀) from 1 to 10 cSt at 100° C. asdetermined by ASTM D-445, a viscosity index (VI) from −100 to 300 asdetermined by ASTM D-2270, and a Noack volatility of no greater than 50percent as determined by ASTM D-5800; wherein said one or more glycolether substituted aryl compounds are produced by a process comprisingreacting a substituted or unsubstituted aryl halide with a substitutedor unsubstituted glycol ether, optionally in the presence of a catalyst,under reaction conditions sufficient to produce said one or more glycolether substituted aryl compounds.

6. A composition comprising one or more glycol ether substituted arylcompounds represented by the formulaR₁—O—R₂wherein R₁ is a substituted or unsubstituted aryl or polyaryl grouphaving from 4 to 40 carbon atoms, and R₂ is the residue of a substitutedor unsubstituted glycol ether having from 4 to 40 carbon atoms; whereinsaid composition has a viscosity (Kv₁₀₀) from 1 to 10 cSt at 100° C. asdetermined by ASTM D-445, a viscosity index (VI) from −100 to 300 asdetermined by ASTM D-2270, and a Noack volatility of no greater than 50percent as determined by ASTM D-5800; wherein said one or more glycolether substituted aryl compounds are produced by a process comprisingreacting a substituted or unsubstituted aryl alcohol with a substitutedor unsubstituted glycol ether halide, optionally in the presence of acatalyst, under reaction conditions sufficient to produce said one ormore glycol ether substituted aryl compounds.

7. A lubricating oil base stock comprising one or more compoundsrepresented by the formulaR₁—O—R₂wherein R₁ is a substituted or unsubstituted aryl or polyaryl grouphaving from 4 to 40 carbon atoms, and R₂ is the residue of a substitutedor unsubstituted glycol ether having from 4 to 40 carbon atoms; whereinsaid lubricating oil base stock has a viscosity (Kv₁₀₀) from 1 to 10 cStat 100° C. as determined by ASTM D-445, a viscosity index (VI) from −100to 300 as determined by ASTM D-2270, and a Noack volatility of nogreater than 50 percent as determined by ASTM D-5800.

8. The lubricating oil base stock of clause 7 wherein R₁ is substitutedor unsubstituted phenyl, benzyl, naphthyl, or diphenyl, and R₂ is theresidue of a substituted or unsubstituted glycol ether (C₄-C₄₀).

9. The lubricating oil base stock of clauses 7 and 8 which is selectedfrom one or more compounds represented by the formulae

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms; and n is a value from 1 to 12;

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms, n is a value from 1 to 12; and X is CH₂, O, NR′ or S,wherein R′ is hydrogen or an alkyl group having from 1 to 4 carbonatoms; and

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms; and n is a value from 1 to 12.

10. The lubricating oil base stock of clauses 7-9 which is selected from1-((2-(2-(hexyloxy)ethoxy)ethoxy)naphthalene,

-   2-(2-(2-(dodecyloxy)ethoxy)ethoxy)benzene,-   (2-(2-hexyloxy)ethoxy)ethoxy)benzene,    1-(2-(2-(hexyloxy)ethoxy)ethoxy)-4-methylbenzene,    4-(2-(2-(hexyloxy)ethoxy)ethoxy)-1,2-dimethylbenzene,    4-(2-(2-(hexyloxy)ethoxy)ethoxy)-N-phenylaniline,    1-(2-(2-(hexyloxy)ethoxy)ethoxy)-4-phenoxybenzene,    1-(2-(2-butoxyethoxy)ethoxy)naphthalene, and-   3-(2-ethoxyethoxyethoxy)-2,6-diphenylmethane.

11. A lubricating oil comprising a lubricating oil base stock as a majorcomponent, and a glycol ether substituted aryl compound cobase stock asa minor component; wherein said glycol ether substituted aryl compoundcobase stock comprises one or more compounds represented by the formulaR₁—O—R₂wherein R₁ is a substituted or unsubstituted aryl or polyaryl grouphaving from 4 to 40 carbon atoms, and R₂ is the residue of a substitutedor unsubstituted glycol ether having from 4 to 40 carbon atoms; whereinsaid lubricating oil has a viscosity (Kv₁₀₀) from 1 to 10 cSt at 100° C.as determined by ASTM D-445, a viscosity index (VI) from −100 to 300 asdetermined by ASTM D-2270, and a Noack volatility of no greater than 50percent as determined by ASTM D-5800.

12. The lubricating oil of clause 11 wherein, in the glycol ethersubstituted aryl compound cobase stock, R₁ is substituted orunsubstituted phenyl, benzyl, naphthyl, or diphenyl, and R₂ is theresidue of a substituted or unsubstituted glycol ether (C₄-C₄₀).

13. The lubricating oil of clauses 11 and 12 wherein the glycol ethersubstituted aryl compound cobase stock is selected from one or morecompounds represented by the formulae

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms; and n is a value from 1 to 12;

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms, n is a value from 1 to 12; and X is CH₂, O, NR′ or S,wherein R′ is hydrogen or an alkyl group having from 1 to 4 carbonatoms; and

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms; and n is a value from 1 to 12.

14. The lubricating oil of clauses 11-13 wherein the glycol ethersubstituted aryl compound cobase stock is selected from1-((2-(2-(hexyloxy)ethoxy)ethoxy)naphthalene,

-   2-(2-(2-(dodecyloxy)ethoxy)ethoxy)benzene,-   (2-(2-hexyloxy)ethoxy)ethoxy)benzene,    1-(2-(2-(hexyloxy)ethoxy)ethoxy)-4-methylbenzene,    4-(2-(2-(hexyloxy)ethoxy)ethoxy)-1,2-dimethylbenzene,    4-(2-(2-(hexyloxy)ethoxy)ethoxy)-N-phenylaniline,    1-(2-(2-(hexyloxy)ethoxy)ethoxy)-4-phenoxybenzene,    1-(2-(2-butoxyethoxy)ethoxy)naphthalene, and-   3-(2-ethoxyethoxyethoxy)-2,6-diphenylmethane.

15. A method for improving one or more of oxidative stability,solubility and dispersancy of polar additives of a lubricating oil byusing as the lubricating oil a formulated oil comprising a lubricatingoil base stock as a major component, and glycol ether substituted arylcompound cobase stock as a minor component; wherein said glycol ethersubstituted aryl compound cobase stock comprises one or more compoundsrepresented by the formulaR₁—O—R₂wherein R₁ is a substituted or unsubstituted aryl or polyaryl grouphaving from 4 to 40 carbon atoms, and R₂ is the residue of a substitutedor unsubstituted glycol ether having from 4 to 40 carbon atoms; whereinsaid lubricating oil has a viscosity (Kv₁₀₀) from 1 to 10 cSt at 100° C.as determined by ASTM D-445, a viscosity index (VI) from −100 to 300 asdetermined by ASTM D-2270, and a Noack volatility of no greater than 50percent as determined by ASTM D-5800.

All patents and patent applications, test procedures (such as ASTMmethods, UL methods, and the like), and other documents cited herein arefully incorporated by reference to the extent such disclosure is notinconsistent with this disclosure and for all jurisdictions in whichsuch incorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.While the illustrative embodiments of the disclosure have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of thedisclosure. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present disclosure,including all features which would be treated as equivalents thereof bythose skilled in the art to which the disclosure pertains.

The present disclosure has been described above with reference tonumerous embodiments and specific examples. Many variations will suggestthemselves to those skilled in this art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims.

The invention claimed is:
 1. A composition comprising one or morecompounds represented by the formula

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms, n is a value from 1 to 12; and X is CH₂, O, NR′ or S,wherein R′ is hydrogen or an alkyl group having from 1 to 4 carbonatoms; wherein said composition has a viscosity (Kv₁₀₀) from 1 to 10 cStat 100° C. as determined by ASTM D-445, a viscosity index (VI) from −100to 300 as determined by ASTM D-2270, and a Noack volatility of nogreater than 50 percent as determined by ASTM D-5800.
 2. The compositionof claim 1 which is 3-(2-ethoxyethoxyethoxy)-2,6-diphenylmethane.
 3. Thecomposition of claim 1 which has a viscosity (Kv₁₀₀) from 2 to 8 cSt at100° C. as determined by ASTM D-445, a viscosity index (VI) from 25 to125 as determined by ASTM D-2270, and a Noack volatility of no greaterthan 25 percent as determined by ASTM D-5800.
 4. A compositioncomprising one or more glycol ether substituted aryl compoundsrepresented by the formula

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms, n is a value from 1 to 12; and X is CH₂, O, NR′ or S,wherein R′ is hydrogen or an alkyl group having from 1 to 4 carbonatoms; wherein said composition has a viscosity (Kv₁₀₀) from 1 to 10 cStat 100° C. as determined by ASTM D-445, a viscosity index (VI) from −100to 300 as determined by ASTM D-2270, and a Noack volatility of nogreater than 50 percent as determined by ASTM D-5800; wherein said oneor more glycol ether substituted aryl compounds are produced by aprocess comprising reacting a substituted or unsubstituted aryl halidewith a substituted or unsubstituted glycol ether, optionally in thepresence of a catalyst, under reaction conditions sufficient to producesaid one or more glycol ether substituted aryl compounds.
 5. Acomposition comprising one or more glycol ether substituted arylcompounds represented by the formula

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms, n is a value from 1 to 12; and X is CH₂, O, NR′ or S,wherein R′ is hydrogen or an alkyl group having from 1 to 4 carbonatoms; wherein said composition has a viscosity (Kv₁₀₀) from 1 to 10 cStat 100° C. as determined by ASTM D-445, a viscosity index (VI) from −100to 300 as determined by ASTM D-2270, and a Noack volatility of nogreater than 50 percent as determined by ASTM D-5800; wherein said oneor more glycol ether substituted aryl compounds are produced by aprocess comprising reacting a substituted or unsubstituted aryl alcoholwith a substituted or unsubstituted glycol ether halide, optionally inthe presence of a catalyst, under reaction conditions sufficient toproduce said one or more glycol ether substituted aryl compounds.
 6. Alubricating oil base stock comprising one or more compounds representedby the formula

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms, n is a value from 1 to 12; and X is CH₂, O, NR′ or S,wherein R′ is hydrogen or an alkyl group having from 1 to 4 carbonatoms; wherein said lubricating oil base stock has a viscosity (Kv₁₀₀)from 1 to 10 cSt at 100° C. as determined by ASTM D-445, a viscosityindex (VI) from −100 to 300 as determined by ASTM D-2270, and a Noackvolatility of no greater than 50 percent as determined by ASTM D-5800.7. The lubricating oil base stock of claim 6 which is 3-(2-ethoxy ethoxyethoxy)-2,6-diphenylmethane.
 8. The lubricating oil base stock of claim6 which has a viscosity (Kv₁₀₀) from 2 to 8 cSt at 100° C. as determinedby ASTM D-445, a viscosity index (VI) from 25 to 125 as determined byASTM D-2270, and a Noack volatility of no greater than 25 percent asdetermined by ASTM D-5800.
 9. A lubricating oil comprising a lubricatingoil base stock as a major component, and a glycol ether substituted arylcompound cobase stock as a minor component; wherein said glycol ethersubstituted aryl compound cobase stock comprises one or more compoundsrepresented by the formula

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms, n is a value from 1 to 12; and X is CH₂, O, NR′ or S,wherein R′ is hydrogen or an alkyl group having from 1 to 4 carbonatoms; wherein said lubricating oil has a viscosity (Kv₁₀₀) from 1 to 10cSt at 100° C. as determined by ASTM D-445, a viscosity index (VI) from−100 to 300 as determined by ASTM D-2270, and a Noack volatility of nogreater than 50 percent as determined by ASTM D-5800.
 10. Thelubricating oil of claim 9 wherein the lubricating oil base stockcomprises a Group I, II, III, IV or V base oil stock.
 11. Thelubricating oil of claim 9 wherein the lubricating oil base stockcomprises a polyalphaolefin (PAO) or gas-to-liquid (GTL) oil base stock.12. The lubricating oil of claim 9 wherein the lubricating oil basestock is present in an amount from 50 weight percent to 99 weightpercent, and the glycol ether substituted aryl compound cobase stock ispresent in an amount from 1 weight percent to 30 weight percent, basedon the total weight of the lubricating oil.
 13. The lubricating oil ofclaim 9 wherein the glycol ether substituted aryl compound cobase stockis 3-(2-ethoxy ethoxy ethoxy)-2,6-diphenylmethane.
 14. The lubricatingoil of claim 9 which has a viscosity (Kv₁₀₀) from 2 to 8 cSt at 100° C.as determined by ASTM D-445, a viscosity index (VI) from 25 to 125 asdetermined by ASTM D-2270, and a Noack volatility of no greater than 25percent as determined by ASTM D-5800.
 15. A method for improving one ormore of oxidative stability, solubility and dispersancy of polaradditives of a lubricating oil by using as the lubricating oil aformulated oil comprising a lubricating oil base stock as a majorcomponent, and glycol ether substituted aryl compound cobase stock as aminor component; wherein said glycol ether substituted aryl compoundcobase stock comprises one or more compounds represented by the formula

wherein R is a substituted or unsubstituted alkyl group having from 4 to40 carbon atoms, n is a value from 1 to 12; and X is CH₂, O, NR′ or S,wherein R′ is hydrogen or an alkyl group having from 1 to 4 carbonatoms; wherein said lubricating oil has a viscosity (Kv₁₀₀) from 1 to 10cSt at 100° C. as determined by ASTM D-445, a viscosity index (VI) from−100 to 300 as determined by ASTM D-2270, and a Noack volatility of nogreater than 50 percent as determined by ASTM D-5800.
 16. The method ofclaim 15 wherein the glycol ether substituted aryl compound cobase stockis 3-(2-ethoxyethoxyethoxy)-2,6-diphenylmethane.
 17. The method of claim15 wherein the glycol ether substituted aryl compound cobase stock has aviscosity (Kv₁₀₀) from 2 to 8 cSt at 100° C. as determined by ASTMD-445, a viscosity index (VI) from 25 to 125 as determined by ASTMD-2270, and a Noack volatility of no greater than 25 percent asdetermined by ASTM D-5800.